Color photography utilizing color couplers which yield quinone imine or azamethine dye images



United States Patent 3 383,214 COLOR PHOTOGRAPI IY UTILIZING COLOR COU- PLERS WHICH iZiELD QUINGNE IMINE 0R AZA- METHINE DYE IMAGES Brian Anderson, Marple, England, assignor to Iiford Limited, Iiford, England, a British company No Drawing. Filed Feb. 15, 1965, Ser. No. 432,898 Claims priority, application Great Britain, Feb. 2%, 1964, 7,180/64 4 Qlaims. (Cl. 96-74) ABSTRACT OF THE DISCLUSURE Color couplers and their use in photographic colloid silver halide emulsions are disclosed. The color couplers are compounds of the formula or the corresponding cyclised compounds, wherein A is a trivalent monocyclic or dicyclic aryl, with the COOH and CONHB groups ortho or peri to each other, X is hydrogen or lower alkyl, Y is OC, CONH or -COCH when X is hydrogen and Y is O S when X is lower alkyl, B is a residue of a compound BNH which will react with the oxidation products of N,N-diethyl .p'phenylene diamine, formed during the development with a silver salt image with that compound, to yield a quinone imine or azamethine dye image and R is a substituent comprising an alkyl group containing at least 12 carbon atoms.

This invention relates to color couplers and to their production and use in color photography.

Many modern processes of color photography are based on the development of a developable silver salt photographic image by means of an aromatic primary amino compound, such as an N,N-diethyl p-phenylene diamine or a derivative thereof in the presence of a so-called color coupler, this being a compound which will couple with the oxidation products of the developer to yield a dye image, usually an azamethine or quinonone-imine dye image, in situ with the developed silver.

Where, as in many of the processes, the color coupler is incorporated in the photographic emulsion layer in which the image is ultimately to be formed, it is important that it should be non-diffusing in such layer, i.e. that it should neither diffuse away during the processing steps nor migrate from its layer to any adjacent layer. Many attempts have been made to achieve this characteristic of non-diifusibility, i.e. to make the color coupler substantive to the medium, usually gelatin, of the photographic emulsion. The methods which have been employed consist generally in the use of color couplers containing groups of substantial molecular size, e.g. long chain alkyl groups, and also solubiiising groups. Such color couplers are often manufactured by a synthesis which involves several stages and the color couplers are usually difiicult to isolate and purify. It is one object of the present invention to provide a new class of color couplers which are non-diffusing in photographic emulsion layers, and which may be manufactured by a simple synthetic process in which a solubilising group and a group conferring nondiffusion are introduced simultaneously and usually in the final stage of the synthesis. Also the solubilising group in the new couplers may be in a protected form Which often facilitates the isolation and purification of the color couplers. The solubilising groups are readily freed when the compounds are dissolved in alkali prior to the addition to the photographic emulsion, or, if the color couplers are applied as a dispersion, in the alkaline developing bath.

According to a first feature of the present invention there is provided, as a new class of color couplers, compounds of the general Formula I:

i RNY-AC O NH-B CODE 1 where the -COOH is ortho or peri to the CONHB group and the corresponding cyclisetl compounds of the general Formula H:

where A is a trivalent radical selected from B is a color coupling residue, X is H or lower alkyl, Y is OC, CONH or -COCH when X is H, and Y is O S when X is lower alkyl, and R is an alkyl group of 12 or more carbon atoms or a group containing same.

By the term color coupler residue used to define the symbol B is meant a grouping such that the compound B-H (and therefore also the compound B.NH is a compound which will react with the oxidation products of N,N-diethyl-p-phenylene diamine, formed during the development of a silver salt image with that compound, to yield a quinone-imine or azamethine dyestuif.

According to a further feature of the invention, color couplers of the general Formula I are obtained by condensing a compound of Formula III:

III wherein R, X, Y and A have the meanings assigned to them above, with a compound B.NH where B has the meaning assigned to it above, at a temperature below C. for example, in boiling ethyl acetate. If the condensation is carried out at higher temperatures and preferably in a solvent such as acetic acid at the boil, then color couplers of Formula II are obtained.

According to another feature of the invention, compounds of Formula II are obtained from compounds of Formula I by heating compounds of Formula I in a solvent at a temperature greater than 100 C. and preferably in glacial acetic acid at the boil.

According to another feature of the invention, compounds of Formula I are obtained from compounds of Formula II by treating with alkali, in a solvent such as a lower alcohol, for example n-propanol, followed by acidification.

The color couplers containing an amino groupie. compounds B-NH which may be used in the process of the invention are for example:

(1) Those which contain a -COCH CO-- group, for example benzoyl-4-amino-2-methoxyacetanilide, 4'-methoxybenzoylacet-4-amino-2-methoxyanilide, the 2-alkoxybenzoylacet amino-anilides described in British patent specification No. 595,314 or the aminobenzoylacet-methoxy-anilides of British patent specification No. 800,108, and which give yellow dyestuffs on color development with substituted p-phenylene diamines.

(2)Those which contain a cyanacetyl group or a pyrazolone ring for example 4-w-cyanacetylaniline, 1-methyl-3- amino-S-pyrazoline, l-(fi-hydroxyethyl)-3-amino-5-pyrazolone, 1-phenyl-3-amino-5-pyrazolone and substituted 1-aryl-3-amino-S-pyrazolones as described in British patent specification Nos. 547,064, 680,474, 680,488, the 1-heterocyclo-3-amino-5-pyrazolones as described in British patent specification No. 599,919, the 1-(aminoaryl)- 3-coumarilylamino-5-pyrazolones of British patent specification No. 890,305, the 1-alkyl-3-(aminophenoxyacetamido)-5-pyrazolones of British patent specification No. 865,720.

(3) Phenols and l-naphthols, which contain an amino group, for example 4-chloro-5-methyl-2-aminophenol or the aminophenols described in British patent specifications Nos. 797,141; 754,306; l-amino-S-naphthol, N(B- aminoethyl)-l-hydroxy-2-naphthamide or similar N-substituted naphthamides containing an amino group, as described in British patent specification No. 902,266 which may also be substituted in the 4-position, as described in British patent specification No. 757,368 and which give cyan dyestuffs on color development with substituted p-phenylene diamines.

It is a preferred feature of the invention to include the new color couplers of the invention in a light-sensitive gelatino or gelatino-substituted silver halide emulsion layer which forms part of a multilayer film or paper of the kind used for color photography.

According to a further feature of the present invention, therefore, there are provided photographic light sensitive colloid silver halide emulsions, which comprise a color coupler of general Formula I or II.

According to a still further feature of the invention there is provided a photographic material for use in color photography which comprises a support carrying a plurality of photographic light sensitive colloid silver halide emulsion layers, selectively sensitive to different regions of the spectrum and comprising in a said emulsion layer or in a layer adjacent thereto, a color coupler of the general Formula I or II.

In the foregoing forms of the invention the colloid will generally be gelatin or may be another colloid medium, e.g. polyvinyl alcohol.

The multilayer color photographic material may be a natural order material in which the images are to be formed in colors complementary to those of the original object or one in which an unnatural order is used, for example one in which in the top layer there is formed a yellow image of the blue parts of the object, in one of the two lower layers there is formed a cyan image of the green parts of the object and in the other a magenta image of the red parts of the object.

The new color couplers may be incorporated in the photographic emulsion layers by taken them up in dilute alkali, e.g. dilute sodium hydroxide and adding the resulting solution to the emulsion. If the color couplers are of Formula II the alkali has the effect of opening the ring structure:

to afford a free carboxylic group.

Alternatively, the compounds may be dispersed, for

example in a non-solvent medium, and the dispersion added to the photographic emulsion.

The following examples will serve to illustrate the invention.

EXAMPLE 1 4- (4-dodecylphenylaminocarbonyl -N-( l-phenyl- 5 -pyraZolonyl-3 phthalimide A mixture of 5.25 parts of 1-phenyl-3-amino-5-pyrazolone, 13.5 parts of 4-(4-dodecylphenylaminocarbonyl) phthalic anhydride and 200 parts of glacial acetic acid is heated under reflux for 1 hour. The reaction product which crystallises out on cooling is filtered off and washed well with ethyl acetate. The 8.4 parts of 4-(4-dodecylphenylaminocarbonyl) N (1 phenyl 5 pyrazolonyl- 3-)phthalirnide are obtained as a fawn colored solid melting at 22-225 C. On analysis the compound is found to contain 73.5% of carbon, 6.7% of hydrogen and 9.2% of nitrogen (C H N O requires 73.0% of carbon, 6.8% of hydrogen and 9.5% of nitrogen).

The 4-(4-dodecylphenylaminocarbonyl)phthalic anhydride used in the above example may be prepared as follows:

A mixture of 50 parts of 4-(4-dodecylphenylaminocarbonyl)phthalic acid and 500 parts of thionyl chloride is heated together under reflux for 2 hours. The yellow crystalline precipitate obtained on cooling is filtered off and recrystallised from 1800 parts of ethyl acetate. The 31 parts of 4-(4-dodecylphenylaminocarbonyl) phthalic anhydride are obtained as a yellow crystalline solid melting at 196 C. On analysis the compound is found to contain 74.1% of carbon, 6.8% of hydrogen and 3.3% of nitrogen (C H NO requires 74.5% of carbon, 7.6% of hydrogen and 3.2% of nitrogen).

The 4-(4-dodecylphenylaminocarbonyl)phthalic acid itself may be prepared as follows:

A mixture of 60 parts of p-dodecylaniline, 48 parts of phthalimide-4-carboxy chloride and 500 parts of dioxan is refluxed for 4 hours. The yellow reaction product which crystallises out on cooling is filtered off and recrystallised from 750 parts of dimethylforrnamide. The 75.0 parts of 4-(4 dodecylphenylaminocarbonyl)phthalimide are obtained as a yellow coloured solid melting at 304- 306 C. On analysis the compound is found to contain 74.8% of carbon, 7.7% of hydrogen and 6.2% of nitrogen. (C H N O requires 74.7% of carbon, 7.8% of hydrogen and 6.4% of nitrogen).

The phthalimide-4-carboxy chloride itself may be obtained from trimellitic anhydride by reacting first with ammonia and then with thionyl chloride.

A photographic layer containing the color coupler may be obtained in the following manner:

A mixture of 1.41 parts of the color coupler, 20 parts of n-propanol and 2.4 parts of 2 N potassium hydroxide solution is warmed to dissolve and distilled water added to make 30 parts. The solution of color coupler so obtained is added to 500 parts of a green sensitised gelatin silver halide emulsion containing silver halide equivalent to 2.5 parts of silver and 3.5% gelatin. The emulsion is then coated on a paper base and the coated layer dried. The photographic layer so obtained is exposed to green light, developed in a colour developer containing 4-amino-N-ethyl-N-E-hydroxypentyl-aniline, bleached and fixed, a magenta image is obtained which has an absorption maximum at a wavelength of light of 536 m 3,333,214 6 EXAMPLE 2 A mixture of 5.25 parts of 1-phenyl-3-amino-5-pyrazo- 2 carboxy 4 (4 dodecylphenylaminocarbonyl) N [3 lone, 13.25 parts of 4-(n-octadecylannnocarbonyl)phthalt h ic anhydride and 250 parts of glacial acetic acid is heated g g figz 4 met oxyphenyl] under reflux for 2 hours. The reaction product which OCH;

omoQ-coomoormQ NHO OQ-C ONHQ-Cnfln HOOC A mixture of 9.42 parts of 4-methoxy-3-(4-methoxycrystallises out on cooling, is filtered 'ofl and recrystallized benzoylacetamide)aniline, 13.05 parts of 4 (4-dodecylfrom 200 ml. of glacial acetic acid. The 10.4 parts of phenylaminocarbonyl) phthalic anhydride and 240 parts 4-(n-octadecylaminocrabonyl) N ('1-phenyl-5-pyrazoof ethyl acetate is refluxed together for 1 hour. The lonyl-3-)phthalimide are obtained as a light brown solid reaction product obtained on cooling is filtered olf and melting at 176-180 C. On analysis the compound is recrystallised from 2000, parts of methanol. The 12.4 found to contain 71.6% of carbon, 7.8% of hydrogen and parts of 2-carboxy-4-(4-dodecylphenylaminocarbonyl)-N- 9.2% of nitrogen (C H N O requires 72.0% of carbon, [3-(4 methoxybenzoylacetarnide) 4 methoxyphenyl] 8.0% of hydrogen and 9.3% of nitrogen). benzamide are obtained as a colourless solid melting at The 4-(n-octadecylaminocarbonyl)phthalic anhydride 216-218 C. On analysis the compound is found to conused in the above example may be prepared as follows: tain 68.3% of carbon, 6.4% of hydrogen and 5.6% of A mixture of 50 parts of 4-(n-octadecylaminocarnitrogen 44 s1 s a ICHaOH requires of bonyl)phthalic acid and 500 parts of acetyl chloride is 13011, 6.9% Of hydroge and g heated under reflux for /2 hour. The colourless crystals EXAMPLE 3 which separate on cooling are collected by filtration and 4-(4-dodecylphenylaminocarbonyl)-N-[}8(1-hydroxy-2- recrystallised from benzene. The 215 parts of 4 (n-octanaphthamido)ethyl]phthalimide. 'decylaminocarbonyl)phthalic anhydride are obtained as A mixture of 6.9 parts of N-(,B-aminoethyl)-1-hydroxya colourless crystalline solid melting at 1 22- 123 C. On 2-naphthamide, 13.05 parts of 4-(4-dodecylphenylamino- 40 analysis the compound is found to contain 72.3% of carbonyl)phthalic anhydride, 240 parts of ethyl acetate carbon, 9.1% of hydrogen, and 3.1% of nitrogen and 15 mls. of glacial acetic acid is refluxed together for (C H N0 requires 73.2% of carbon, 9.2% of hydro- 1 hour. The solid reaction product obtained on cooling gen and 3.1% of nitrogen). is filtered oif, heated under reflux with 900 parts of acetic The 4-(n-octadecylaminocarbonyl)phthalic acid itselt acid, cooled and collected by filtration. 10.0 parts of 4- 45 may be repar d as f ll (4-dodecylphenylaminocarbonyl) N [6(1 hydroxy- A mixture of 51 parts of 4-(n-octadecylaminocarbonyl) 2 naphthamido)ethyl]phthalimide are obtained melting phthalimide, 125 parts of 2N sodium hydroxide solution, at 274-275 C. On analysis the compound is found to 750 parts of water and 500 parts of ethanol is heated contain 74.4% of carbon, 7.0% of hydrogen and 6.7% under reflux for 3 hours. The solution obtained is after of nitrogen (C H -N O requires 74.4% of carbon, cooling acidified with 210 parts of 2 N hydrochloric acid 7.0% of hydrogen and 6.5% of nitrogen). and the colorless solid precipitated, is collected by filtra- A photographic layer containing the color coupler may tion and recrystallised from 300 parts of glacial acetic be obtained in the following manner: acid. The 53.2 parts of 4-(n-octadecylaiminocarbonyl) A mixture of 2.4 parts of the color coupler, 16 parts phthalic acid are obtained as a colorless solid melting at of n-propyl alcohol and 3.6 parts of 2 N potassium hy- 55 125-127 C.

droxide solution is heated to the boil to dissolve and The 4-(n-octadecylaminocarbonyl)phthalimide used then diluted to 40 parts with distilled water. The solution sb i prepared as follows;

so obtained is added to 500 parts of a red sensitised A mi ture of 50.3 parts of phthalimide-4-carboxy ch1 gelatino silver halide emulsion containing silver halide ride 92 parts f o tadecylamine and 1,000 parts of q 'fi to Parts of Silver and 35% gelatin The dioxan is stirred under reflux for 3 hours. The solution emulsl n 1 then coatedon base and the is cooled and the precipitated solid collected by filtration. layer drled- When the photographic layer 80 Obtamed 18 After drying the solid is heated with 700 ml. of benzene olour develo er 2 32x5311? 4 g gi figfi g elflllyzrgxyphenylanflgle, and the suspension filtered hot, the residue is then crystalbleached and fixed, a cyan image is obtained which has li'sed from dimethylformamide. The 51.5 parts of 4-(nan absorption maximum at a wavelength of light of ootadecylarninoearbonyl)phthalimide are obtained as a 670 mw solid melting at 228-231" C. On analysis the compound EXAMP 4 is found to contain 73.0% of car-hon, 9.0% of hydrogen 4-(n-octadecylaminocarbonyl)-N-(I-phenyl S- and 6.2% of nitrogen (C2qH42NO3 requires 73.3% of PY Y carbon, 9.5% of hydrogen and 6.3% of nitrogen).

A photographic layer which contains 1.43 parts of the above color coupler, formulated by the method of Ex- C- cfin CONH OmH37 ample 1 gives a magenta dye image with light absorption 00 maximum at 531 millimicrons.

7 EXAMPLE 4-(n-ootadecylaminocarbonyl)-N- [[i( l-hydroxy- 2-napl1thamido)ethyl]phthalimido A mixture of 3.45 parts of N-(B-aminoethyD-l-hydroxy-Z-naphthamide, 6.64 parts of 4-( n-octadecylaminocarbonyDphthalic anhydride and 150 parts of glacial acetic acid is heated under reflux for 1 /2 hours. The solid reaction product obtained is collected by filtration and recrystallised from dimethyl formamide. The 8.6 parts of 4 (n-octadecylaminocarbonyl) N [[3 (=1-hydroxy-2- naphthamido)ethyl1phthalimide are obtained as a solid melting at 257-258 C. On analysis the compound is found to contain 72.6% of carbon, 8.1% of hydrogen and 6.4% of nitrogen (C H N O requires 73.3% of carbon, 8.1% of hydrogen and 6.4% of nitrogen).

A photographic layer which contains 2.36 parts of the above color coupler, formulated by the method of Example 3 gives a cyan dye image with light absorption maximum at 670 millimicrons.

-CONHCmIIn C0 EXAMPLE 6 4-(n-octadecylaminocarbonyD-N-[3-(4-methoxybenzoylacetamido) -4-methoxy phenyl1pht-halimide i C ONHCmHu droxide solution is heated to the boil to dissolve and then diluted to 100 parts with distilled water. The solution so obtained is added to 400 parts of a blue sensitized gelatino silver halide emulsion containing silver halide equivalent to 10 parts of silver and 22.5 parts of gelatin. The emulsion is then coated on a paper base and the coated layer dried. When the photographic paper so obtained is exposed to blue light, developed in a color developer containing 4-amino-N-ethyl-N-e-hydroxypentylaniline a yellow image is obtained which has an absorption maximum of light at 434 millim-ocrons.

EXAMPIJE 7 4-(4-dodecylphenylaminocarb onyl) -N(4-wcyanacetylphenyl) phthalimide In place of the 5.25 parts of 1-phenyl-3-amino-5- pyrazolone used in Example 1 there are used 4.4 parts of 4-w-cyanacetylaniline. The 13.9 parts of 4-(4-dodecylphenylaminocarbonyl) N (4 w cyanacetylephenyl) phenyl)phthalimide are obtained as a solid melting at 222-224" C. On analysis the compound is found to contain 7.0% of carbon, 6.5% of hydrogen and 7.2% of nitrogen (C H N O requires 74.9% of carbon, 6.8% of hydrogen and 7.3% of nitrogen).

A photographic layer which contains 1.35 parts of the above color coupler, formulated by the method of Example 1 gives a magenta dye image with maximum light absorption at 500 millimicrons.

EXAMPLE 8 4-(4-dodecylphenylaminocarb onyl -N-4-methoxy-3- [N- l-phenyl-5-pyrazolonyl-3-)amino] phenyl phthalimide H 0 CH3 A mixture of 7.85 parts of 4-methoxy-3-(4-methoxybenzoylace-tamido) aniline, 11.05 parts of 4-(n-octadecylaminoca'rbonynphthalic anhydride and 250 parts of glacial acetic acid is heated under reflux for 2 hours. The reaction product whichcrystallises out on cooling is collected by filtration and recrystallised from ethyl acetate. The 7.1 parts of 4-(n-octadecylaminocarbonyl)-N-[3-(4- methoxybenzoylacetamido) 4 methoxyphenyl1phthalimide are obtained as a solid melting at l-l55 C. On analysis the compound is found to contain 71.3% of carbon, 7.9% of hydrogen and 5.6% of nitrogen (C44I I57N3O7 requires 71.5% of carbon, 7.7% of hydrogen and 5.8% of nitrogen).

A photographic layer containing the color coupler may be obtained in the following manner:

A mixture of 5. l2 parts of color coupler, 16 parts of n-propyl alcohol and 695 parts of 2 N potassium hy- EXAMPLE 9' 4-(4-dodecylphenylaminocarbonyl) -N-{4- [N- l-phenyl- 5-pyrazolonyl-3-) aminoacetyl1phenyl} phthalimide CONHQ-Cnllzn In place of the 5.25 parts of 1-phenyl-3-amino-5-pyrazolone used in Example 1 there are used 9.25 parts of 1-phenyl-3-(4-aminophenyl acetylamino)5-pyrazone, the preparation of which is described in British patent specification No. 830,797. The coupler is filtered ofl from the reaction mixture and recrystallised from glacial acetic acid. The 15.2 parts of 4-(4-dodecylphenylaminocarbonyl) N {4-[N-(1-phenyl-5-pyrazolonyl-3-)aminoacetyl] phenyl} phthalimide are obtained as a solid melting at 238-240 C.

A photographic layer which contains 1.7 parts of the above color coupler, formulated by method of Example 1 gives a magenta dye image with maximum light absorption at 500 millimicrons.

EXAMPLE 10 4- (4-dodecylphenylaminocarbonyl -N- [4-(4-methoxybenzoylacetamido phenyl] phthalimide omo-Q-oo CH2 0 o NHN\ A mixture of 7.1 parts of 4-(4-methoxybenzoylacetamido) aniline, 10.9 parts of 4-(4-dodecylphenylaminocarbonyl)phthalic anhydride and 500 parts of glacial acetic acid is heated under reflux for 2 hours. After cooling the solid is filtered off and washed well with ethyl acetate. The 14 parts of 4-(4-dodecylphenylaminocarbonyl)-N-[4- methoxybenzoylacetamido phenyl] phthalimide are obtained as a solid melting at 2'69-274 C. On analysis the compound is found to contain 73.7% of carbon, 6.8% of hydrogen and 5.9% of nitrogen (C H N O requires 73.6% of carbon, 6.7% of hydrogen and 6.0% of nitrogen).

A photographic layer which contains 4.85 parts of the above coupler, formulated by the method of Example 6 gives a yellow dye image with maximum light absorption at 438 millimicrons.

EXAMPLE l-1 4-(4-dodecylphenylaminocarbonyl) -N-3-[ (4-chloro-1-hy- -droxy-2-naphthamido)methyl]phenyl phthalimide (in CO In place of the 5.25 parts of 1-phenyl-3-amino-5pyrazolone used in Example 1 there are used 10.0 parts of 4-chloro -'1 hydroxy-Z-N-(3-aminobenzyl)naphthamide. The product is filtered off from the cold reaction mixture and recrystallised from ethyl acetate. The 19.2 parts of the coupler are obtained as a solid melting at 22723*1 C. on analysis the compound is found to contain 72.0% of carbon, 5.7% of hydrogen and 5.3% of nitrogen (C H N CIO requires 72.7% of carbon, 6.2% of hydrogen).

The 4-chloro-1-hydr0xy-2-N-(3-aminobenzyl)naphthamide used in the above example may be prepared as follows:

A mixture of 20 parts of 1-hydroxy-4-chloro-2-N-(3-nitrobenzyl) naphthamide, 80 parts of ethyl alcohol and 20 parts of hydrazine hydrate is heated under reflux and Raney nickel catalyst added. After the vigorous reaction has subsided, the R-aney nickel is filtered off and the fil- CONH 10 trates evaporated to dryness in vacuo, the residue is then recrystallised from methyl alcohol containing a little sodium dithionite. The 4-chloro-1-hydroxy-2-N-(3-aminobenZyDna htha-mide is obtained as pale fawn crystals melting at 162-'164 C.

The 1 hydroxy-4-chloro-2-N-(3-nitrobenzyl)naphthamide itself may be prepared as follows:

A mixture of 15.2 parts of 3-nitrobenzylamine and 29.8 parts of phenyl:l-hydroxy-4-chloro-2-naphthoate is heated at 160170 C. at a pressure of 12 mm. and the phenol formed is distilled off. After cooling the reaction mixture is stirred with methanol, filtered and recrystallised by dissolving in 100 parts of Sellosolve and adding parts of ethanol and 50 parts of water. The 15.8 parts of 4-chloro- 1-hydroxy-2-N(3-nitrobenzyl)napthamide are obtained as a solid melting at 192-194 C.

A photographic layer which contains 2.7 parts of the above coupler, formulated by the method of Example 3 gives a cyan dye image with maximum light absorption at 678 millimicrons.

EXAMPLE 12 2-carboxy-N-(1-phenyl-5-pyrazolonyl-3)-benzamide- 4-N'-methyl-N'- (4-dodecylphenyl) sulphonamide A mixture of 5.25 parts of 1-phenyl-3-amino-5-pyrazolone, 14.5 parts of phthalic anhydride-4-N-methyl-N-(4- dodecylphenyl)sulphonamide and 240 parts of glacial acetic acid is heated at 60 C. for 1 hour. The product which crystallises out of the reaction mixture on standing for 12 hours is recrystallised from 500 parts of ethanol. The 11.1 parts of 2-carboxy-N-(l-phenyl-S-pyrazolonyl- 3-) benzamide-4-N-methyl-N' (4 dodecylphenyl) sulphonamide are obtained as a solid melting at 167-170" C. On analysis the product is found to contain 65.6% of carbon, 6.5% of hydrogen, 8.4% of nitrogen and 5.2% of sulphur (C H N O S requires 65.5% of carbon, 6.7% of hydrogen, 8.5% of nitrogen and 4.85% of sulphur).

The phthalic anhydride 4 N-methyl-N-(4-dodecylphenyl)sulphonamide used in the above example may be prepared as follows:

A mixture of 36 parts of phthalic acid-4-N-methyl-N- (dodecylphenyl)sulphonamide and 400 parts of acetyl chloride is heated under reflux for 30 minutes and then evaporated to dryness in vacuo. The residue is recrystallised twice of 60-80 grade petroleum ether. The 28 parts of phthalic anhydride-4-N-methyl-N-(4-dodecylphenyl) sulphonamide are obtained as colourless solid melting at 107108 C. On analysis the compound is found to contain 66.2% of carbon, 7.2% of hydrogen, 2.9% of nitrogen and 6.7% of sulphur (C H NO S requires 66.8%

1 1 of carbon, 7.2% of hydrogen, 2.9% of nitrogen and 6.6% of sulphur).

The phthalic acid-4-N-methyl-N-(4-dodecylphenyl)sulphonamide may be prepared as follows:

A mixture of 39 parts of phthalic acid-4-N-(4-dodecylphenyl)sulphonamide, 12.9 parts of potassium hydroxide pellets, 380 parts of water and 32.6 parts of methyl iodide is stirred at 20 C. for 1 hour then at 50 C. for 1 hour. The mixture is acidified with 2N hydrochloric acid solution, the colourless precipitate collected by filtration and recrystallised from 50:50 water/ acetic acid mixture. The 38 parts of phthalic acid-4-N-methyl-N-(4-dodecylphenyl) sulphonamide are obtained as a colorless solid melting at l45-146 C. On analysis the compound is found to contain 64.9% of carbon, 7.0% of hydrogen, 2.8% of nitrogen and 6.6% of sulphur (C27H3'1NO6S requires 64.5% of carbon, 7.4% of hydrogen, 2.8% of nitrogen and 6.4% of sulphur).

A photographic layer which contains 1.57 parts of the above coupler, formulated by the method of Example 1 gives a magenta dye image with maximum light absorption at 530 millimicrons.

Q I H EXAMPLE 13 2 carboxy N-[3-(4-methoxybenzoylacetamido)-4-methoxyphenyl]benzamide 4 N'-rnethyl N'-(4-dodecyl) sulphonamide A mixture of 9.4 parts of 4-methoxy-3-(4-methoxybenzoylacetamido)aniline, 14.5 parts of phthalic anhydride-4- N-methyl-N-(4-dodecy1phenyl)sulphonamide and 150 parts ethyl acetate is heated at 60 C. for 1 hour.

The solution obtained is poured into 800 parts of petroleum ether to precipitate the coupler, the product is filtered off and recrystallised from 150 parts of methyl alcohol. The 18.9 parts of 2-carboxy-N-[3-(4-methoxybenzoylacetamido) 4 methoxyphenyHbenzarnide 4- N'-(4-dodecylphenyl)sulphonamide are obtained as a solid melting at l24-125 C. On analysis the compound is found to contain 64.5% of carbon, 6.1% of hydrogen, 5.1% of nitrogen and 4.0% of sulphur (C H N SO requires 66.0% of carbon, 6.6% of hydrogen, 5.25% of nitrogen and 4.0% of sulphur).

A photographic layer which contains 5.54 parts of the above coupler, formulated by the method of Example 6 gives a yellow dye image with maximum light absorption at 438 millimicrons.

12 EXAMPLE 14 2 carboxy-N-[[3-( l-hydroxy-Z-naphthamido)ethyl] benzamidc-4-N'-methyl-N'-(4-dodecylphenyl sulphonamide H on:

HOOC

A mixture of 10.05 parts of N-(fi-aminoethyD-l-hydroxy-Z-naphtharnide, 16.95 parts of phthalic anhydride- 4-N-methyl N (dodecylphenyl)sulphonamide and 250 parts of ethyl acetate is heated at 60 C. for 1 hour, the solution is then evaporated down in vacuo to a small volume. The product which crystallises out is collected by filtration and washed with methanol. The 12.5 parts of 2- carboxy N[/8 (1 hydroxy 2 naphthamido)ethyl] benzamide 4 N' methyl N (4 dodecylphenyl)sulphonamide are obtained as a solid melting at 158-160 C. On analysis the compounds is found to contain 66.7% of carbon, 6.5% of hydrogen, 6.1% of nitrogen and 4.6% of sulphur (C H N O S requires 67.1% of carbon, 6.8% hydrogen, 5.9% of nitrogen and 4.5% of sulphur).

phenyl 5 pyrazolonyl 3-)-aminocarbonyl]-4-chlorophenyl}benzimide C-NHO C Q NHO o-Q-comrQmm HOOC A mixture of 3.28 parts of 1-phenyl-3-(3-amino-4-chloro)benzylamino-5-pyrazolone, 4.35 parts of 4-(4-dodecylphenylaminocarbonyl)phthalie anhydride and 75 parts of ethyl or ethyl acetate is heated under reflux for 2 hours.

The product which crystallises out on cooling is collected by filtration and extracted twice with methanol. The 4.6 parts of 2-carboxy-4-(4-dodecylphenylaminocarbonyl)-N- {3-[1-phenyl-(5-pyrazolonyl-3)aminocarbonyl] 4 chlorophenyl}benzamide are obtained as a solid melting at 236 C. On analysis the compound is found to contain 67.3% of carbon, 7.3% of hydrogen, 9.5% of nitrogen and 5.0% of chlorine (C H N O Cl requires 67.6% of carbon, 6.0% of hydrogen, 9.2% of nitrogen and 4.7% of chlorine).

The 1-phenyl-3-(3-amino 4 chloro)benzoylamino-5- pyrazolone used in the above example may be prepared as follows:

40 parts of 1-phenyl-3-(3-nitro-4-chloro)benzoylamino- S-pyrazolone are dissolved in 500 parts of ethyl acetate and reduced with hydrogen at C. over Raney nickel catalyst. The product is filtered off, dissolved in n-propyl alcohol by warming and filtered to separate the catalyst. The solution is then evaporated in vacuo to a small vol- 13 ume and the product which crystallises out is collected by filtration. The 23.7 parts of 1phenyl-3-(3-amino-4-chloro)benzoylamine-S-pyrazolone are obtained as a solid melting at 210-211 C. On analysis the compound is found to contain 58.6% of carbon, 4.2% of hydrogen,

16.5% of nitrogen and 11.0% of chlorine (C H N O Cl requires 58.4% of carbon, 4.0% of hydrogen, 17.0% of nitrogen and 10.8% of chlorine).

The 1 phenyl-3-(3-nitro-4-chloro)benzoylamino-5-py razolone itself may be prepared as follows:

* A rnixture of 13.4 parts of 5-nitro-2-chlorobenzoyl chlo- I ride, parts of 1-phenyl-3-amino-5-pyrazolone and 10 parts of diethyl oxalate is heated on a steam bath for 10 minutes, 50 parts of ethyl alcohol are then added to the solidified mixture and the heating continued for a further minutes. The product is collected by filtration and extracted' twice with methyl alcohol. The 13 parts of 1- phenyl-3-(3-nitro-4-chloro)benzoylamino 5 pyrazolone are obtained as a solid melting at 210-215 C.

The S-nitro-Z-chlorobenzoyl chloride may be obtained 20 by heating S-nitro-Z-chlorobenzoic acid with thionyl chloride.

EXAMPLE l6 3 -carboxy-4- [4-5- 1 -hydroxy-2-naphtharnido ethyl phenyl] aminocarbonyl-N- (4-dodecylphenyl benzamide 8.7 parts of 4-(4-d0decylphenylaminocarbonyl)phthalic anhydride and 6.1 parts of 4-(p-amino-fl-phenylethyl)-1- hydroxynaphthamide as described in U.S. Patent 2,589,-

004 are heated under reflux with 100 parts by volume of 40 dry ethyl acetate for 15-30 minutes. Complete solution is not achieved. On cooling and filtering otT the solid and washing with a little ethyl acetate, 14.6 parts of 3-carboxy-4-[4-fl-(1-hydroxy 2 naphthamido)ethyl phenyl] aminocarbonyl-N-(4-dodecyl phenylphenyhbenzamide are obtained, M.P. 266 dec. On analysis, this compound is found to contain 73.7% of carbon, 6.7% of hydrogen and 6.0% of nitrogen (C H N O requires 74.5% of carbon, 6.9% of hydrogen and 5.7% of n itrogen).

A photographic emulsion layer which contains 2.67 parts of the above color coupler, formulated by the method of Example 3 gives a cyan dye image with a light absorption maximum at 684 millimicrons.

o o NET-@OnHzs 35 8.7 parts of 4-(4-dodecylphenylaminocarbon)phthalic an- 8.7 parts of 4-(4-dodecylphenylaminocarbonyl)phthalic anhydride and 6.1 parts of 2-(o-amino-B-phenylethyl)-1- hydroxynaphthamide as described in U.S. Patent 3,002,- 836 are heated under reflux with 100 parts by volume of dry ethyl acetate for 15-30 minutes. Complete solution is not achieved. On cooling and filtering off the solid and washing with a little ethyl acetate, 13.0 parts of 3-carboxy-4-[2-[3-(l-hydroxy 2 naphthamido)ethyl phenyl] aminocarbonyl N (4-dodecylphenyl)benzamide are obtained as a colorless powder M.P. 196 dec. On analysis, this compound is found to contain 75.0% of carbon, 7.0% of hydrogen and 5.5% of nitrogen (C H N O requires 74.5% of carbon, 6.9% of hydrogen and 5.7% of nitrogen).

A photographic emulsion layer which contains 2.67 parts of the above color coupler, formulated by the method of Example 3 gives a cyan dye image with a light absorption maximum at 690 millimicrons.

EXAMPLE 18 3-carboxy-4-[6-(1-hydroxy-2-naphthamido)hexyl] aminocarbonyl-N- (4-dodecyl phenyl benzamide COOH hydride and 5.7 parts of 1-(l-hydroxy-Z-naphthamido)-6- aminohexane are heated under reflux with 100 parts by volume of dry ethyl acetate for 15-30 minutes. On cooling and filtering oi? the solid deposited 12.4 parts of 3- carboxy-4-[6-(1-hydroxy 2 naphtharnido)hexyl]aminocarbonyl N (4-dodecylphenyl)benzamide are obtained, M.P. 182 dec. On analysis, this compound is found to contain 7.4% of hydrogen and 5.8% of nitrogen (C H N O requires 7.6% of hydrogen and 5.8% of a nitrogen).

A photographic emulsion layer which contains 2.60 parts of the above color coupler, formulated by the method of Example 3 gives a cyan dye image with a light absorption maximum at 680 millirnicrons.

EXAMPLE 19 3-carboxy-4-[2-[3-(1-hydroxy-4-chloro 2 naphthamido) ethyl phenylJamino carbonyl N (4 dodecylphenyl) benzamide EXAMPLE 17 3-carboxy-4- [2-5- 1-hydroxy-2-naphthamido ethyl phenyl] aminocarbonyl-N- (4-dodecylphenyl benzamide C O O H OH NHCO CONHCH2CH2- OH NHCO 5.9 parts of 4 (4-dodecylphenylaminocarbonyl)phthalic anhydride and 4.5 parts of 2-(-o amino-fi-pheny-lethyl)-lhydroxy-4-chloronaphthamide are heated under reflux with '100 parts by volume of dry ethyl acetate for 20 minutes. Complete solution is not achieved. On cooling and filtering off the solid and washing with a little ethyl acetate, 9.0 parts of 3-carboxy-4-[2-fl-(1-hydroxy-4- chlor-o-2-naphthamido)ethyl phenyl] aminocarbonyl-N- (4-dodecylphenyl)henzamide are obtained M.P. 198-l99 dec. On analysis, this compound is found to contain 71.2% of carbon, 6.4% of hydrogen, 5.4% of nitrogen and 4.4% of chlorine (C H ClN O requires 71.1% of carbon, 6.4% of hydrogen, 5.4% of nitrogen and 4.6% of chlorine).

'A photographic emulsion layer which contains 2180 parts of the above color coupler, formulated by the method of Example 3 gives a cyan dye image with light absorption maximum of 690 millimicrons.

I claim:

1. A photographic colloid silver halide emulsion containing a color coupler which is a compound selected from the class consisting of compounds of the Formula I:

where A is a trivalent radical selected from the class consisting of and in the case where A is the COOH group is ortho to the CONHB group and in the case where A is the COOH group is in one of the positions ortho and peri to the CONHB group, X is selected from the class consisting of hydrogen andlower alkyl, Y is selected from the class consisting of the linkages OC--, CONH and COCH when X is hydrogen and Y is O S- when X is lower alkyl, B is a residue of a compound BNH which will react with the oxidation products of N,N-diethyl p-phenylene diamine, formed during the development with a silver salt image with that compound, to yield a dyestufi image selected from the class consisting of quinone imine and azamethine dyes, said compound BNH being selected from the class consisting of such compounds wherein B contains a COCH -CO- group and the compound gives a yellow dyestulf on color development with substituted p-phenylene diamines, such compounds wherein B contains a cyanacetyl group and the compound gives a magenta dyestufi? on said color development, such compounds wherein B contains a pyrazolone ring and the compound gives a magenta dyestulf on said color development, and such compounds wherein B is a phenolic residue and the compound gives a cyan image on said color development, and such compounds wherein B is a naphtholic residue and the compound gives a cyan image on said color development, and R is a swbstituent comprising an alkyl group containing at least 12 carbon 16 atoms and corresponding cylised compounds of the Formula II:

t R-N-Y-A N-B wherein R, X, Y and B have the meanings just assigned and A is a trivalent radical selected from the class conand in the case where A is the two -'CO- groups are ortho to each other and in the case where A is the two CO- linkages are in one of the positions ortho and peri to each other.

2. A photographic colloid silver halide emulsion according to claim 1 in which the colloid is gelatin.

3. A photographic material for use in color photography which comprises a support carrying a plurality of photographic light sensitive colloid silver halide emulsion layers selectively sensitive to difierent regions of the spectrum said material containing in operative-contact with said emulsion layer a color coupler which is a compound selected from the class consisting of compounds of the Formula I:

X R-IL-Y-A-C o NH-B where A is a trivalent radical selected from the class consisting of:

and

in the case where A is the COOH group is ortho to the CONHB group and in the case where A is the -COOH group is in one of the positions ortho and peri to the CONHB group, X is selected from the class consisting of hydrogen and lower .alkyl, Y is selected from the class consisting of the linkages OC-, CONH and COCH when X is hydrogen and Y is O S when X is lower alkyl, B is a residue of a compound BNH which will react with the oxidation products of N,N-diethyl p-phenylene diamine, formed during the development with a silver salt image with that compound, to yield a dyestutf image selected from the class consisting of quinone imine and azamethine dyes, said compound BNH being selected from the class consisting of such compounds wherein B contains a -COCH CO- group and the compound gives a yellow dyestutf on color development with substituted p-phenylene diamines, such compounds wherein B contains a cyanacetyl group and the compound gives a magenta dyestuff on said color development, such compounds wherein B contains a pyrazolone ring and the compound gives a magenta dyestuif on said color development, and such compounds wherein B is a phenolic residue and the compound gives a cyan image on said color development, and such compounds wherein B is a naphtholic residue and the compound gives a cyan image on said color development, and R is a substituent comprising an alkyl group containing at least l2 carbon atoms and corresponding cyclised compounds of the formula:

wherein R, X, Y and B have the meanings just assigned 13 and A is trivalent radical selected from the class consisting of and in the case where A is the two CO groups are ortho to each other and in the case where A is the two CO- linkages are in one of the positions ortho and peri to each other.

4. -A photographic material according to claim 3 wherein the colloid of the emulsion layers is gelatin.

J. TRAVIS BROWN, Primary Examiner. 

